A POLYMER COATED SULPHUR CURED RUBBER COMPOSITION

Abstract

There is disclosed a method of forming a polymer coated sulphur cured rubber composition wherein the bond strength between the polymer coating and the sulphur cured rubber is surprisingly great. The method includes providing a sulphur curable rubber composition comprising a compound including at least one thiol group, and/or contacting a sulphur curable rubber composition with a compound including at least one thiol group, and contacting the sulphur curable composition with a second polymeric precursor including a diallylamide group. The compound including at least one thiol group and the second polymeric precursors are reacted together to form a polymeric layer; and the sulphur curable rubber composition is cured to form a polymer coated sulphur cured rubber composition.

Claims

1. A method of forming a polymer coated sulphur cured rubber composition including: providing a sulphur curable rubber composition comprising a compound including at least one thiol group, and/or contacting a sulphur curable rubber composition with a compound including at least one thiol group, contacting the sulphur curable composition with a second polymeric precursor including a compound of formula A or II: ##STR00007## wherein R.sup.6 represents an amine moiety, a quaternary ammonium cation or an optionally substituted hydrocarbyl group, R.sup.20 represents an optionally substituted hydrocarbyl group, each of R.sup.1 and R.sup.2 independently represents an optionally substituted hydrocarbyl group, j is an integer from 1 to 4; ##STR00008## wherein each of R.sup.1 and R.sup.2 independently represents an optionally substituted hydrocarbyl group, R.sup.17 and R.sup.18 independently represents an optionally substituted hydrocarbyl group, or hydrogen, y is an integer of from 1 to 3; z is an integer of from 1 to 3; wherein the combination of the integers represented by y and z must be 4 or less, and where the combination of the integers represented by y and z is 3, one of R.sup.17 and R.sup.18 is absent, and where the combination of the integers represented by y and z is 4, both of R.sup.17 and R.sup.18 are absent; X.sup. represents a counter ion; reacting the compound including at least one thiol group and the second polymeric precursors to form a polymeric layer; and curing the sulphur curable rubber composition to form a polymer coated sulphur cured rubber composition.

2. The method as claimed in claim 1, wherein the method comprises disposing the compound including at least one thiol group between the sulphur curable rubber composition and a substrate and/or within the sulphur curable rubber composition; disposing the second polymeric precursor between the sulphur curable rubber composition and the substrate.

3. The method as claimed in claim 1 wherein the compound including at least one thiol group comprises an optionally substituted hydrocarbyl group and one to eight thiol groups.

4. The method as claimed in claim 3 wherein the hydrocarbyl group of the compound including at least one thiol group is substituted with one or more ether, ketone, ester, silane, amide and/or amine groups.

5. The method as claimed in claim 4 wherein the hydrocarbyl group of the compound including at least one thiol group is substituted with one or more ester, ether and/or amide groups.

6. The method as claimed in claim 1 wherein the compound including at least one thiol group does not include any functional groups except for thiol which react under the conditions used to react the compound including at least one thiol group and the second polymeric precursor to form a polymeric layer.

7. The method as claimed in claim 1 wherein the ratio of diallylamide groups of the second polymeric precursor to thiol groups which react to form the polymeric layer is 1:1.5 to 25.

8. The method as claimed in claim 1 wherein the second polymeric precursor includes a compound of formula I ##STR00009## wherein each of R.sup.17 to R.sup.19 independently represents an optionally substituted hydrocarbyl group, or hydrogen; R.sup.20 represents an optionally substituted hydrocarbyl group each of R.sup.1 and R.sup.2 independently represents an optionally substituted hydrocarbyl group, j is an integer from 1 to 4; X.sup. represents a counter ion.

9. The method as claimed in claim 1 wherein the sulphur curable composition includes 0.5 to 10 wt. % sulphur.

10. The method as claimed in claim 1 wherein the composition comprising the compound including at least one thiol group includes less than 0.1 wt. % isocyanate.

11. The method as claimed in claim 1 wherein the sulphur curable composition comprises the compound including at least one thiol group.

12. The method of claim 11 wherein the sulphur curable rubber composition and the compound including at least one thiol group are provided in a solution.

13. The method of claim 2, wherein the substrate is contacted with the second polymeric precursor and the coated substrate is then contacted with the compound including at least one thiol group (or vice versa) prior to the coated substrate being disposed proximate to the sulphur curable rubber composition.

14. The method of claim 13 wherein the compound including at least one thiol group and/or the second polymeric precursors are cured on the substrate prior to the coated substrate being disposed proximate to the sulphur curable rubber composition.

15. A composite including a substrate, a sulphur cured rubber and a polymeric layer disposed therebetween, wherein the polymeric layer is formed through the reaction of a compound including at least one thiol group, and a second polymeric precursor including a compound of Formula A or II, wherein the compound having the structure of Formula A is ##STR00010## wherein R.sup.6 represents an amine moiety, a quaternary ammonium cation or an optionally substituted hydrocarbyl group, R.sup.20 represents an optionally substituted hydrocarbyl group, each of R.sup.1 and R.sup.2 independently represents an optionally substituted hydrocarbyl group, j is an integer from 1 to 4; and wherein the compound having the structure of Formula II is ##STR00011## wherein each of R.sup.1 and R.sup.2 independently represents an optionally substituted hydrocarbyl group, R.sup.17 and R.sup.18 independently represents an optionally substituted hydrocarbyl group, or hydrogen, y is an integer of from 1 to 3; z is an integer of from 1 to 3; wherein the combination of the integers represented by y and z must be 4 or less, and where the combination of the integers represented by y and z is 3, one of R.sup.17 and 10 is absent, and where the combination of the integers represented by y and z is 4, both of R.sup.17 and 10 are absent; X.sup. represents a counter ion.

16. The composite of claim 15 wherein the polymeric layer is bonded to the sulphur cured rubber through covalent bonds.

17. The composite as claimed in claim 15 including more than one layer of sulphur cured rubber, and/or more than one layer of substrate, wherein each layer of the composite is bonded to adjacent layer(s) with the polymeric layer formed through the reaction of the compound including at least one thiol group and the second polymeric precursor.

18. An emulsion including an oil phase comprising the compound including at least one thiol group and an aqueous phase comprising the second polymeric precursor including a compound of Formula A or II, wherein the compound having the structure of Formula A is ##STR00012## wherein R.sup.6 represents an amine moiety, a quaternary ammonium cation or an optionally substituted hydrocarbyl group, R.sup.20 represents an optionally substituted hydrocarbyl group, each of R.sup.1 and R.sup.2 independently represents an optionally substituted hydrocarbyl group, j is an integer from 1 to 4; and wherein the compound having the structure of Formula II is ##STR00013## wherein each of R.sup.1 and R.sup.2 independently represents an optionally substituted hydrocarbyl group, R.sup.17 and R.sup.18 independently represents an optionally substituted hydrocarbyl group, or hydrogen, y is an integer of from 1 to 3; z is an integer of from 1 to 3; wherein the combination of the integers represented by y and z must be 4 or less, and where the combination of the integers represented by y and z is 3, one of R.sup.17 and R.sup.18 is absent, and where the combination of the integers represented by y and z is 4, both of R.sup.17 and R.sup.18 are absent; and X.sup. represents a counter ion.

19. An aqueous composition comprising the compound including at least one thiol group and the second polymeric precursor including a compound of Formula A or II, wherein the compound having the structure of Formula A is ##STR00014## wherein R.sup.6 represents an amine moiety, a quaternary ammonium cation or an optionally substituted hydrocarbyl group, R.sup.20 represents an optionally substituted hydrocarbyl group, each of R.sup.1 and R.sup.2 independently represents an optionally substituted hydrocarbyl group, j is an integer from 1 to 4; and wherein the compound having the structure of Formula II is ##STR00015## wherein each of R.sup.1 and R.sup.2 independently represents an optionally substituted hydrocarbyl group, R.sup.17 and R.sup.18 independently represents an optionally substituted hydrocarbyl group, or hydrogen, y is an integer of from 1 to 3; z is an integer of from 1 to 3; wherein the combination of the integers represented by y and z must be 4 or less, and where the combination of the integers represented by y and z is 3, one of R.sup.17 and R.sup.18 is absent, and where the combination of the integers represented by y and z is 4, both of R.sup.17 and R.sup.18 are absent; and X.sup. represents a counter ion.

20. (canceled)

Description

[0228] The present invention will now be described by way of example only with reference to the following figures in which:

[0229] FIG. 1 shows the peel strength of a polymeric layer formed from polymeric precursor of formula A disposed between a sulphur cured styrene butadiene rubber layer and a nylon layer in a styrene butadiene rubber-nylon laminate;

[0230] FIG. 2 shows the peel strength of a polymeric layer formed from polymeric precursor pentaerythritol tetra (3-mercaptopropionate)(PETMP) disposed between a sulphur cured styrene butadiene rubber layer and a nylon layer in a styrene butadiene rubber-nylon laminate;

[0231] FIG. 3 shows the peel strength of a polymeric layer formed from the polymeric precursor of formula A of FIG. 1 and from polymeric precursor pentaerythritol tetra (3-mercaptopropionate) (PETMP) disposed between a sulphur cured styrene butadiene rubber layer and a nylon layer in a styrene butadiene rubber-nylon laminate;

[0232] FIG. 4 shows the peel strength of a control sulphur cured styrene butadiene rubber-nylon laminate without a polymeric layer disposed between the styrene butadiene rubber and the nylon layers;

[0233] FIG. 5 shows the peel strength of a polymeric layer formed from polymeric precursor comprising compounds of formula I disposed between a styrene butadiene rubber and a nylon layer in a styrene butadiene rubber-nylon composite;

[0234] FIG. 6 shows the peel strength of a polymeric layer formed from thiol PETMP disposed between a styrene butadiene rubber layer and a nylon layer in a styrene butadiene rubber-nylon composite;

[0235] FIG. 7 shows the peel strength of a polymeric layer formed from the polymeric precursor comprising compounds of formula I of FIG. 5 and from polymeric precursor thiol PETMP disposed between a styrene butadiene rubber layer and a nylon layer in a styrene butadiene rubber-nylon composite;

[0236] FIG. 8 shows the peel strength of a control styrene butadiene rubber-nylon laminate without a polymeric layer disposed between the styrene butadiene rubber and the nylon layers;

[0237] FIG. 9 shows the peel strength of a polymeric layer formed from polymeric precursor comprising compounds of formula I of FIG. 5 and from polymeric precursor thiol PETMP in a fully aqueous system disposed between a styrene butadiene rubber layer and a nylon layer in a styrene butadiene rubber-nylon composite;

[0238] FIG. 10 shows the peel strength of a polymeric layer formed from polymeric precursor comprising compounds of formula I of FIG. 5 and from polymeric precursor thiol PETMP disposed between a styrene butadiene rubber layer and a nylon layer in a styrene butadiene rubber-nylon composite wherein the ratio of diallylamide groups:thiol groups was 1.0:20.3;

[0239] FIG. 11 shows the peel strength of a polymeric layer formed from polymeric precursor comprising compounds of formula I of FIG. 5 and from polymeric precursor thiol PETMP disposed between a styrene butadiene rubber layer and a nylon layer in a styrene butadiene rubber-nylon composite wherein the ratio of diallylamide groups:thiol groups was 1.0:10.6;

[0240] FIG. 12 shows the peel strength of a polymeric layer formed from polymeric precursor comprising compounds of formula I of FIG. 5 and from polymeric precursor thiol PETMP disposed between a styrene butadiene rubber layer and a nylon layer in a styrene butadiene rubber-nylon composite wherein the ratio of diallylamide groups:thiol groups was 1.0:5.7;

[0241] FIG. 13 shows the peel strength of a polymeric layer formed from polymeric precursor comprising compounds of formula I of FIG. 5 and from polymeric precursor thiol PETMP disposed between a styrene butadiene rubber layer and a nylon layer in a styrene butadiene rubber-nylon composite wherein the ratio of diallylamide groups:thiol groups was 1.0:2.4;

[0242] FIG. 14 shows the peel strength of a polymeric layer formed from polymeric precursor comprising compounds of formula I of FIG. 5 and from polymeric precursor thiol PETMP disposed between a styrene butadiene rubber layer and a nylon layer in a styrene butadiene rubber-nylon composite wherein the ratio of diallylamide:thiol groups was 1.0:1.6.

EXAMPLE 1a

[0243] A composition including a polymeric precursor of formula A was applied to a nylon sheet. The coated nylon sheet was placed next to unvulcanised sulphur curable SBR. Heat and pressure were applied to each side of the resultant laminate to cure the SBR and to polymerise the polymeric precursor of formula A. A styrene butadiene rubber-nylon laminate comprising a polymeric layer formed from the polymeric precursor of formula A disposed between a sulphur cured SBR layer and a nylon layer was formed accordingly.

[0244] Specimens 25 mm wide were cut from the resultant laminate, and the strength of the polymeric layer was tested using the standard test method for peel resistance for adhesives, namely the T-peel test. The laminated test panels were peeled at a constant head speed of 254 mm/min. The results are provided in FIG. 1 and the table 1a below:

TABLE-US-00001 TABLE 1a First Peak Min Peel Max Peel Average Average Load Load Load Load Load/Width [N] [N] [N] [N] [N/m] 1 12.26 5.81 12.26 7.38 295.27 2 11.08 6.29 11.08 7.48 299.02 3 15.55 6.11 15.55 7.71 308.43 4 12.68 6.42 12.68 7.73 309.32 5 13.58 6.24 13.58 8.17 326.80 Mean 13.03 6.17 13.03 7.69 307.77 Standard 1.67 0.23 1.67 0.31 12.23 deviation The average load per unit width of the polymeric layer was 307.77 N/m (standard deviation 12.23 N/m).

EXAMPLE 1b

[0245] The method of Example 1a was repeated substituting the polymeric precursor of formula A with a composition including PETMP. Specimens 25 mm wide were cut from the resultant laminate, and the strength of the polymeric layer was tested using the T-peel test. The results are provided in FIG. 2 and the table 1b below:

TABLE-US-00002 TABLE 1b First Peak Min Peel Max Peel Average Average Load Load Load Load Load/Width [N] [N] [N] [N] [N/m] 1 34.04 15.54 34.04 18.82 752.78 2 32.86 15.93 32.86 19.89 795.44 3 29.85 16.09 30.38 19.46 778.22 4 24.19 14.08 25.10 17.46 698.21 5 23.16 13.33 23.16 17.56 702.39 Mean 28.82 14.99 29.11 18.64 745.41 Standard 4.95 1.22 4.78 1.10 43.91 deviation The average load per unit width of the polymeric layer was 745.41 N/m (standard deviation 43.91 N/m).

EXAMPLE 1c

[0246] The method of Example 1a was repeated but the textile was contacted first with the composition including the polymeric precursor of formula A of Example 1a and then with the PETMP composition of Example 1b. Specimens 25 mm wide were cut from the resultant laminate, and the strength of the polymeric layer was tested using the T-peel test. The results are provided in FIG. 3 and the table 1c below:

TABLE-US-00003 TABLE 1c First Peak Min Peel Max Peel Average Average Load Load Load Load Load/Width [N] [N] [N] [N] [N/m] 1 278.04 240.10 431.72 350.85 14034.17 2 542.05 10.53 542.05 387.37 15494.98 3 572.92 352.53 572.92 422.12 16884.92 4 549.26 367.76 562.86 433.19 17327.49 5 455.21 333.91 455.21 392.30 15692.12 Mean 479.50 260.97 512.95 397.17 15886.73 Standard 121.12 148.54 64.94 32.34 1293.78 deviation The average load per unit width of the polymeric layer was 15,886.73 N/m (standard deviation 1,293.78 N/m). This demonstrates a very surprising synergistic effect from application of the thiol containing compound and the diallylamide polymeric precursor. The bond strength of the polymeric layer increased by around 2000%.

EXAMPLE 1d

[0247] For completeness, as a control the method of Example 1a was repeated with no polymeric layer between the nylon layer and the sulphur cured rubber composition. The nylon layer was adhered to the rubber during curing thereof. Specimens 25 mm wide were cut from the resultant laminate, and the strength of the bond between the rubber composition and the nylon layer was tested using the T-peel test. The results are provided in FIG. 4 and the table 1d below:

TABLE-US-00004 TABLE 1d First Peak Min Peel Max Peel Average Average Load Load Load Load Load/Width [N] [N] [N] [N] [N/m] 1 10.35 3.96 10.35 5.24 209.70 2 9.16 3.93 9.16 5.05 201.81 3 10.98 4.79 10.98 5.62 224.96 4 9.66 4.21 9.66 4.96 198.45 5 9.93 4.53 9.93 5.65 225.84 Mean 10.01 4.28 10.01 5.30 212.15 Standard 0.69 0.37 0.69 0.32 12.77 deviation The average load per unit width of the polymeric layer was 212.15 N/m (standard deviation 12.77 N/m).

EXAMPLE 2a

[0248] The method of Example 1a was repeated wherein the polymeric layer was formed from a composition including a polymeric precursor of formula I applied to the nylon sheet.

[0249] Specimens 25 mm wide were cut from the resultant laminate, and the strength of the polymeric layer was tested using the T-peel test. The results are provided in FIG. 5 and the table 2a below:

TABLE-US-00005 TABLE 2a First Peak Min Peel Max Peel Average Average Load Load Load Load Load/Width [N] [N] [N] [N] [N/m] 1 17.93 11.79 19.20 15.74 629.43 2 20.94 12.62 21.01 16.43 657.32 3 19.92 13.47 20.83 16.81 672.44 4 20.04 13.31 21.25 17.16 686.25 5 18.57 12.31 22.05 17.58 703.28 6 17.36 12.44 19.03 15.66 626.50 Mean 19.12 12.66 20.56 16.56 662.54 Standard 1.39 0.63 1.20 0.77 30.80 deviation The average load per unit width of the polymeric layer was 662.54 N/m (standard deviation 30.80 N/m).

EXAMPLE 2b

[0250] The method of Example 2a was repeated substituting the composition including the polymeric precursor with a composition including thiol containing compound PETMP. Specimens 25 mm wide were cut from the resultant laminate, and the strength of the polymeric layer was tested using the T-peel test. The results are provided in FIG. 6 and the table 2b below:

TABLE-US-00006 TABLE 2b First Peak Min Peel Max Peel Average Average Load Load Load Load Load/Width [N] [N] [N] [N] [N/m] 1 52.63 19.64 52.63 28.32 1132.65 2 38.43 19.08 44.07 26.35 1054.09 3 40.13 24.67 40.13 30.20 1207.89 4 37.33 24.36 38.60 31.67 1266.73 5 40.35 23.79 56.51 34.28 1371.24 6 43.38 20.95 43.38 27.70 1108.06 Mean 42.04 22.08 45.89 29.75 1190.11 Standard 5.58 2.49 7.13 2.91 116.22 deviation The average load per unit width of the polymeric layer was 1190.11 N/m (standard deviation 116.22 N/m).

EXAMPLE 2c

[0251] The method of Example 2a was repeated but the textile was contacted first with the composition including the polymeric precursor of formula I of Example 2a and then with the composition including thiol PETMP of Example 2b. Specimens 25 mm wide were cut from the resultant laminate, and the strength of the polymeric layer was tested using the T-peel test. The results are provided in FIG. 7 and the table 2c below:

TABLE-US-00007 TABLE 2c First Peak Min Peel Max Peel Average Average Load Load Load Load Load/Width [N] [N] [N] [N] [N/m] 1 299.68 262.76 440.64 333.23 13329.08 2 451.99 279.85 451.99 334.66 13386.22 3 451.76 255.77 451.76 311.14 12445.52 4 348.86 242.28 378.68 310.03 12401.03 5 201.61 189.71 385.21 327.94 13117.57 Mean 350.78 246.08 421.65 323.40 12935.88 Standard 106.43 34.30 36.61 11.97 478.78 deviation The average load per unit width of the polymeric layer was 12,935.88 N/m (standard deviation 478.78 N/m). This demonstrates a synergistic effect from application of the thiol containing compound and the diallylamide polymeric precursor. The bond strength of the polymeric layer increased by around 1000%. In addition, no volatile organic compounds were required.

EXAMPLE 2d

[0252] For completeness, as a control the method of Example 2a was repeated with no polymeric layer between the nylon layer and the sulphur cured rubber composition. The nylon layer was adhered to the rubber during curing thereof. Specimens 25 mm wide were cut from the resultant laminate, and the strength of the adhesive layer was tested using the T-peel test. The results are provided in FIG. 8 and the table 2d below:

TABLE-US-00008 TABLE 2d Loat at Average Load Average Load/Width Peak first at Average at Average (Primary load Minimum Maximum value (5 Peaks value (5 Peaks measurement) Peel Load Peel Load and troughs) and troughs) [N] [N] [N] [N] [N/m] 1 9.31 5.02 9.31 6.29 251.76 2 8.46 5.07 8.46 6.69 267.57 3 7.29 4.79 7.65 6.10 243.89 4 8.85 5.70 8.85 6.80 271.95 5 8.46 5.49 8.46 6.68 267.37 6 8.76 5.66 8.76 6.96 278.43 Mean 8.52 5.29 8.58 6.59 263.49 Standard 0.68 0.38 0.55 0.33 13.02 deviation The average load per unit width of the polymeric layer was 263.49 N/m (standard deviation 13.02 N/m).

EXAMPLE 2e

[0253] The method of Example 2c was repeated wherein the composition including the polymeric precursor of formula I of Example 2a and the composition including the thiol PETMP of Example 2b were aqueous compositions. The concentrations of the compositions remained the same. The results are provided in FIG. 9 and the table 2e below:

TABLE-US-00009 TABLE 2e First Peak Min Peel Max Peel Average Average Load Load Load Load Load/Width [N] [N] [N] [N] [N/m] 1 351.87 228.40 421.80 314.60 12583.88 2 313.41 255.41 428.36 348.23 13929.40 3 407.92 271.57 499.23 344.80 13792.02 4 264.71 242.19 433.98 347.40 13896.10 5 329.81 251.89 433.13 334.02 13360.88 Mean 333.54 249.89 443.30 337.81 13512.45 Standard 52.50 16.01 31.64 14.17 566.66 deviation The average load per unit width of the polymeric layer was 13,513 N/m (standard deviation 567 N/m), again demonstrating a synergistic effect through application of the thiol containing compound and the diallylamide polymeric precursor. The bond strength of the polymeric layer increased by over 1000%. This is a fully aqueous system and unlike other systems known in the art, no drop in bond strength was exhibited when the system was changed from organic to aqueous. In addition, no volatile organic compounds were required.

EXAMPLE 3a

[0254] The method of Example 2c was repeated. The textile was contacted with a composition including the polymeric precursor of formula I of Example 2c and with a composition including thiol PETMP. The ratio of diallylamide groups:thiol groups was 1.0:20.3. Specimens 25 mm wide were cut from the resultant laminate, and the strength of the polymeric layer was tested using the T-peel test. The results are provided in FIG. 10 and the table 3a below:

TABLE-US-00010 TABLE 3a First Peak Min Peel Max Peel Average Average Load Load Load Load Load/Width [N] [N] [N] [N] [N/m] 1 407.24 315.78 482.17 406.79 16271.43 2 469.66 230.38 469.66 341.63 13665.22 3 525.07 203.40 525.07 284.76 11390.55 4 509.21 181.20 509.21 314.76 12590.21 5 248.91 156.26 472.32 280.35 11213.95 Mean 432.02 217.40 491.69 325.66 13026.27 Standard 112.00 61.42 24.35 51.67 2066.97 deviation The average load per unit width of the polymeric layer was 13,026 N/m (standard deviation 2066.97 N/m).

EXAMPLE 3b

[0255] The method of Example 3a was repeated. The textile was contacted with a composition including the polymeric precursor of formula I of Example 3a and with a composition including thiol PETMP. The ratio of diallylamide groups:thiol groups was 1.0:10.6. Specimens 25 mm wide were cut from the resultant laminate, and the strength of the polymeric layer was tested using the T-peel test. The results are provided in FIG. 11 and the table 3b below:

TABLE-US-00011 TABLE 3b First Peak Min Peel Max Peel Average Average Load Load Load Load Load/Width [N] [N] [N] [N] [N/m] 1 334.72 217.88 402.45 311.93 12477.14 2 377.88 327.44 486.47 384.73 15389.28 3 339.82 274.75 520.83 396.65 15866.01 4 336.48 302.30 473.07 398.55 15941.80 5 364.64 272.49 423.65 334.73 13389.11 Mean 350.71 278.97 461.29 365.32 14612.67 Standard 19.42 40.88 47.95 39.52 1580.99 deviation The average load per unit width of the polymeric layer was14,613 N/m (standard deviation 1580.99 N/m).

EXAMPLE 3c

[0256] The method of Example 3a and 3b was repeated. The textile was contacted with a composition including the polymeric precursor of formula I of Example 3a and with a composition including thiol PETMP. The ratio of diallylamide groups:thiol groups was 1.0:5.7. Specimens 25 mm wide were cut from the resultant laminate, and the strength of the polymeric layer was tested using the T-peel test. The results are provided in FIG. 12 and the table 3c below:

TABLE-US-00012 TABLE 3c First Peak Min Peel Max Peel Average Average Load Load Load Load Load/Width [N] [N] [N] [N] [N/m] 1 91.51 69.19 106.61 85.13 3405.01 2 118.35 70.31 118.35 86.37 3454.86 3 127.41 82.50 127.41 97.36 3894.39 4 128.66 94.96 139.50 118.58 4743.30 5 148.57 84.40 148.57 118.47 4738.97 Mean 122.90 80.27 128.09 101.18 4047.31 Standard 20.73 10.72 16.63 16.53 661.39 deviation The average load per unit width of the polymeric layer was 4,047 N/m (standard deviation 661.39 N/m).

EXAMPLE 3d

[0257] The method of Example 3a to 3c was repeated. The textile was contacted with a composition including the polymeric precursor of formula I of Example 3a and with a composition including thiol PETMP. The ratio of diallylamide groups:thiol groups was 1.0:2.4. Specimens 25 mm wide were cut from the resultant laminate, and the strength of the polymeric layer was tested using the T-peel test. The results are provided in FIG. 13 and the table 3d below:

TABLE-US-00013 TABLE 3d First Peak Min Peel Max Peel Average Average Load Load Load Load Load/Width [N] [N] [N] [N] [N/m] 1 71.26 39.77 75.85 54.91 2196.20 2 67.63 33.08 67.63 43.76 1750.40 3 60.04 33.59 65.26 46.99 1879.58 4 60.85 30.52 60.85 43.39 1735.64 5 69.88 37.87 69.88 49.57 1982.63 Mean 65.93 34.97 67.90 47.72 1908.89 Standard 5.18 3.77 5.56 4.74 189.72 deviation The average load per unit width of the polymeric layer was 1,909 N/m (standard deviation 189.72 N/m).

EXAMPLE 3e

[0258] The method of Example 3a to 3d was repeated. The textile was contacted with a composition including the polymeric precursor of formula I of Example 3a and with a composition including thiol PETMP. The ratio of diallylamide:thiol groups was 1.0:1.6. Specimens 25 mm wide were cut from the resultant laminate, and the strength of the polymeric layer was tested using the T-peel test. The results are provided in FIG. 14 and the table 3e below:

TABLE-US-00014 TABLE 3e First Min Max Average Peak Peel Peel Average Load/ Load Load Load Load Width [N] [N] [N] [N] [N/m] 1 34.74 18.13 34.74 22.24 889.55 2 20.78 12.49 22.60 17.48 699.04 3 8.23 7.77 22.56 18.16 726.49 4 3.17 2.60 23.07 17.87 714.80 5 22.58 13.30 22.58 17.98 719.18 Mean 17.90 10.86 25.11 18.75 749.81 Standard 12.49 5.90 5.39 1.97 78.76 deviation The average load per unit width of the polymeric layer was 750 N/m (standard deviation 78.76 N/m).

[0259] Various modifications and variations of the described aspects of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes of carrying out the invention which are obvious to those skilled in the relevant fields are intended to be within the scope of the following Claims.